Isocyanate-Containing Thermoplastic Polyurethane

ABSTRACT

Thermoplastic polyurethane (i) comprising from 20% by weight to 70% by weight of isocyanate dissolved in the thermoplastic polyurethane, based on the total weight of the thermoplastic polyurethane (i) comprising the isocyanates.

The invention relates to a thermoplastic polyurethane (i) comprisingfrom 20% by weight to 70% by weight, preferably from 25% by weight to70% by weight, particularly preferably from 30% by weight to 60% byweight, in particular from 35% by weight to 60% by weight, veryparticularly preferably from 40% by weight to 60% by weight, especiallypreferably from 45% by weight to 55% by weight, of isocyanate dissolvedin the thermoplastic polyurethane, based on the total weight of thethermoplastic polyurethane (i) comprising the isocyanates, and also toprocesses for producing these thermoplastic polyurethanes (i) comprisingisocyanate, in which preference is given to melting thermoplasticpolyurethane and subsequently incorporating the isocyanate into themelt, preferably homogeneously. In addition, the invention relates toprocesses for producing polyurethanes, in which the production iscarried out in the presence of the inventive thermoplastic polyurethanes(i) comprising the isocyanates. Furthermore, the invention relates toprocesses for reacting thermoplastic polyurethanes with isocyanate, forexample in an extruder, in which the inventive thermoplasticpolyurethanes (i) comprising isocyanates are used as isocyanate. Inaddition, the invention relates to processes for injection moldingthermoplastic polyurethane, in which thermoplastic polyurethane isinjection molded together with the inventive thermoplastic polyurethane(i) comprising isocyanates.

The production of thermoplastic polyurethanes, hereinafter referred toas TPUs for short, is generally known.

TPUs are partially crystalline materials and belong to the class ofthermoplastic elastomers. A characteristic of polyurethane elastomers isthe segmented structure of the macromolecules. Owing to the differingcohesion energy densities of these segments, a phase separation intocrystalline “hard” and amorphous “soft” regions occurs in the idealcase. The resulting two-phase structure determines the property profileof TPUs. Thermoplastic polyurethanes are plastics having a wide range ofapplications. Thus, TPUs are used, for example, in the automobileindustry, e.g. in dashboard skins, in films, in cable sheathing, in theleisure industry, as deposition areas, as functional and design elementsin sports shoes, as flexible component in rigid-flexible combinationsand in many further applications.

It is known from the literature that the property profile of TPU can beimproved by introducing crosslinking into the TPU, leading to thestrength being increased, the heat resistance being increased, thetensile and compressive sets being reduced, the resistance to media ofall types, resilience and creep behavior being improved.

Known crosslinking methods are, inter alia, UV or electron beamcrosslinking, crosslinking via siloxane groups and the formation ofcrosslinks by addition of isocyanates to the molten TPU. The reaction ofa TPU, preferably in the molten state, with compounds bearing isocyanategroups is also referred to as prepolymer crosslinking and is generallyknown from U.S. Pat. No. 4,261,946, U.S. Pat. No. 4,347,338, DE-A 41 15508, DE-A 4 412 329, EP-A 922 719, GB 2347933, U.S. Pat. No. 6,142,189,EP-A 1 158 011. Despite this general knowledge of the possible ways ofachieving prepolymer crosslinking, this process has hitherto not beenable to be implemented in industrial practice. A reason for this is,inter alia, the complicated apparatus. Very homogeneous mixing of theTPU, which is generally in the form of pellets, with the liquid orviscous compounds having isocyanate groups leads to considerabledifficulties in practice. Secondly, the reaction of the TPU with thecompounds having isocyanate groups also represents a difficult chemicaltask, since mixing of the molten TPU with diisocyanates can lead to adegradation of the molecular weight of the thermoplastic polyurethanes,while mixing with triisocyanates and polyisocyanates can cause anincrease in the molecular weight as far as crosslinking of thethermoplastic polyurethanes in the extruder. In both cases, reliableprocessing of the polyurethane is made difficult or prevented. On theother hand, very pronounced crosslinking in the end product is sought.

It was an object of the present invention to optimize the chemicalcomponents in such a way that very good process reliability, e.g. meltstability, and very pronounced crosslinking can be achieved. Inaddition, the components should be able to be used, in particular, ininjection molding and lead to articles which can be crosslinked.

These objects can be achieved by carrying out the introduction of theisocyanate by means of the concentrates described at the outset, i.e.the inventive TPU (i) comprising isocyanates in high concentration.

The present invention is distinguished from the prior art by, inparticular, the substantially simplified handling of the isocyanates.While liquid isocyanates have to be handled in most of the documentscited above, according to the present invention it is possible to addsolids in the form of the thermoplastic polyurethanes (i) comprising theisocyanates. The addition of a solid is of particular importance forinjection molding. In addition, the adhesion of a thermoplasticpolyurethane to other thermoplastic polymers in, in particular,2-component injection molding has been able to be substantially improvedby use of the concentrate (i), either alone or together with furtherthermoplastic polyurethane, presumably as a result of the freeisocyanate groups.

In particular, the solid concentrates (i) offer the advantage that thevolatility of the isocyanates is significantly reduced. It hassurprisingly been found that a TPU comprising 50% by weight of aprepolymer based on MDI and having an NCO content of 23% and a viscosityof 650 mPas determined in accordance with DIN 53018 was, firstly,free-flowing and, secondly, no volatile MDI could be detected. Inaddition, the isocyanates are stable in the inventive TPUs (i), i.e.they barely react or do not react at all and are therefore, contrary toexpectations, sufficiently storage-stable.

The inventive thermoplastic polyurethanes (i) comprising the isocyanatescan thus be used and processed like concentrates. While in the prior artthe addition of the isocyanate to the thermoplastic polyurethane iscarried out immediately before processing to the end product andcrosslinking, according to the invention it is possible to produce astable concentrate (i) which can be processed only at a significantlylater point in time together with further thermoplastic polyurethane toform the end product. A distinction is therefore made in the presenttext between the concentrates of the invention, i.e. the thermoplasticpolyurethane (i) comprising the isocyanate, and the “normal”thermoplastic polyurethanes which do not comprise isocyanates in theamounts according to the invention. The concentrates are denoted by (i)in the present text.

In the thermoplastic polyurethanes (i) of the invention, the isocyanatesare present as a solution in the TPU, in particular in the soft phase ofthe thermoplastic polyurethane. Reaction of the isocyanate with the TPUand thus degradation or crosslinking of the TPU can be avoided, inparticular, by a sufficiently low temperature being selected duringincorporation. The molecular weight of the TPU usually does not changeor changes only very slightly during the incorporation according to theinvention of the isocyanates. On the other hand, it is preferred thatthe thermoplastic polyurethane is molten during the incorporation of theisocyanate in order to be able to reach a very high concentration ofisocyanates in the TPU very quickly. The inventive thermoplasticpolyurethane (i) comprising isocyanate is preferably stored at atemperature below 40° C. until it is processed.

The concentrate according to the invention, i.e. the TPU (i) comprisingthe isocyanates, has the additional advantage that no foreign polymer isintroduced on addition to the TPU to be crosslinked. Thus, the TPU to becrosslinked can be admixed with the same TPU (i) comprising theisocyanates. Mixtures can thus be avoided, as can substantialadaptations by means of formulation changes, i.e. by addition of aforeign polymer.

The TPUs of the invention, i.e. the thermoplastic polyurethanes (i)comprising the isocyanates, particularly preferably have an NCO contentof greater than 5%, preferably greater than 8%, particularly preferablyfrom 10% to 40%.

Here, the NCO content is determined as the sum of isocyanate andallophanate. The sample is for this purpose dissolved indimethylformamide comprising the amine and maintained at 80° C. for 4hours. The unreacted excess of amine is backtitrated with acid.

Specifically, the following procedure is employed:

A sample to be tested for isocyanate content is weighed out. The amountweighed out depends on the expected content of isocyanate groups and isweighed to a precision of ±0.001 g. The analysis is carried out as aduplicate determination.

For each analysis, blank determinations without a sample but otherwisecompletely identical are carried out as a triplicate determination.

20.00 ml of a di-n-hexylamine solution (8.8(±0.01)g of di-n-hexylamineare made up with DMF to give 2000 ml of solution) are metered by meansof a Dosimat 665 (Metrohm Dosimat 665 with a 20 ml burette attachment)into a wide-neck bottle (Schott 250 ml laboratory bottles with screwclosure made of PP (blue), DIN thread GL45). 100 ml of DMF are thenadded by means of a Dispensette and the weighed-out sample issubsequently added. The wide-neck bottle is closed firmly and the solidsample comprised therein is then dissolved by means of a magneticstirrer bar (magnetic stirrer bar, triangular, I=55 mm) in the firmlyclosed bottle on an oil bath at 80° on a magnetic stirrer.

In all three cases, the samples are then cooled to room temperature andcan then be titrated.

Three drops of indicator solution (bromophenol blue, 1% in DMF) areadded to the cooled solutions. The solution is then backtitrated with0.1 N hydrochloric acid (prepared by making up the content of an ampouleof Titrisol 0.1 mol/l hydrochloric acid to 1 l with 1-butanol) in1-butanol using a Dosimat 665 (Metrohm Dosimat 665 with 5 ml buretteattachment) The end point is reached when the color changes from lightgreen to yellowish greenish yellow. The acid consumption is denoted by“A” in the calculation.

The mean of the amount of acid consumed in the three blankdeterminations is denoted by “B” in the calculation.

Both analytical values are calculated separately.

Calculation of the total isocyanate content in % of NCO (sum ofisocyanate groups and allophanate groups, calculated as NCO):

W=weight of the sample in g (±0.001 g)

B=consumption of acid in the blank test (mean) in ml

A=consumption of acid in the analysis in ml

% of NCO=(B−A)×0.42/W

The mean of the duplicate determination is the NCO content of the TPUsample (i).

As isocyanates in the thermoplastic polyurethane (i) of the invention,generally known isocyanates, for example aliphatic, cycloaliphaticand/or aromatic isocyanates generally having 2 isocyanate groups, can bepresent. Isocyanates of higher functionality, e.g. polymeric MDI ormodified isocyanates, for example isocyanates which comprise biuretgroups and have from 2 to 10 isocyanate groups, isocyanurates whichpreferably have from 2 to 8, particularly preferably 3, isocyanategroups, and/or prepolymers which have from 2 to 10 isocyanate groups,i.e. isocyanates, and are obtainable by reacting isocyanates withcompounds which are reactive toward isocyanates, generally alcohols, arealso possible.

Examples of possible isocyanates are thus trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene and/or octamethylenediisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene1,4-diisocyanate,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophoronediisocyanate, IPDI), 1,4- and/or 1,3-bis(isocyanatomethyl)cyclohexane(HXDI), cyclohexane 1,4-diisocyanate, 1-methylcycloxane 2,4- and/or2,6-diisocyanate and/or dicyclohexylmethane 4,4′-, 2,4′- and2,2′-diisocyanate, diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate(MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and/or2,6-diisocyanate (TDI), 3,3′-dimethylbiphenyl diisocyanate,1,2-diphenylethane diisocyanate and/or phenylene diisocyanate.

Preference is given to using MDI, a carbodiimide-modifieddiphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI) and/or aprepolymer based on diphenylmethane 2,2′-, 2,4′- and/or4,4′-diisocyanate (MDI), triisocyanates or polyisocyanates, inparticular biurets or isocyanurates of the isocyanates mentioned, inparticular an isocyanurate having an NCO content of from 20% to 25% anda viscosity at 23° C. in the range from 2500 mPas and 4000 mPas, and/ormixtures of diisocyanates and triisocyanates, preferably mixtures (ii)comprising (iia) compounds which have at least three, preferably three,isocyanate groups and are based on aliphatic isocyanates, preferablyhexamethylene diisocyanate (HDI) and/or1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (isophoronediisocyanate, IPDI), particularly preferably hexamethylene diisocyanate(HDI), and (iib) compounds which have two isocyanate groups and arebased on aromatic isocyanates, preferably diphenylmethane 2,2′-, 2,4′-and/or 4,4′-diisocyanate (MDI), particularly preferably diphenylmethane4,4′-diisocyanate. As (iia), preference is given to using anisocyanurate having three isocyanate groups, preferably an isocyanuratebased on HDI, i.e. a trimerized HDI in which three HDI units form anisocyanurate structure and three free isocyanate groups are present.Particular preference is given to using an isocyanurate having an NCOcontent of from 20% to 25%, preferably from 21.5% to 22.5%, and aviscosity at 23° C. in the range from 2500 mPas and 4000 mPas as (iia).As (iib), preference is given to using diphenylmethane 2,2′-, 2,4′-and/or 4,4′-diisocyanate (MDI), a carbodiimide-modified MDI and/or aprepolymer based on MDI. Particular preference is given to using aprepolymer based on diphenylmethane 2,2′-, 2,4′- and/or4,4′-diisocyanate (MDI), alkanediol, preferably dipropylene glycol,having a molecular weight of from 60 g/mol to 400 g/mol and polyetherdiol, preferably polypropylene glycol ether, having a molecular weightof from 500 g/mol to 4000 g/mol as (iib). Particular preference is givento using a prepolymer having a viscosity at 25° C. in the range from 500mPas to 800 mPas, preferably from 550 mPas to 770 mPas, and an NCOcontent of from 20% to 25%, preferably from 22.4% to 23.4%, as (ib).(iia) and (iib) are preferably used in a weight ratio of (iia):(iib) offrom 1:1 to 1:10, preferably from 1:3 to 1:4.

Particularly preferred isocyanates are diphenylmethane 2,2′-, 2,4′-and/or 4,4′-diisocyanate (MDI), a carbodiimide-modified diphenylmethane2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), a prepolymer based ondiphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), preferablya prepolymer having an NGO content of from 20 to 25% and a viscosity at25° C. of from 500 to 1000 mPas determined in accordance with DIN 53018,isocyanates comprising biuret and/or isocyanurate groups, particularlypreferably an isocyanurate having an NCO content of from 20% to 25% anda viscosity at 23° C. of from 2500 mPas and 4000 mPas determined inaccordance with DIN EN ISO 3219, in particular one based onhexamethylene diisocyanate (HDI).

Particular preference is given to carbodiimide-modified diphenylmethane4,4′-diisocyanate (MDI), particularly preferably having an isocyanatecontent of from 25% by weight to 33% by weight, in particular from 29.5%by weight, for example Lupranat® MM 103 (BASF Aktiengesellschaft),prepolymers based on ethylene oxide/propylene oxide, preferably having amolecular weight in the range from 400 to 600 g/mol, in particularM_(w)=450 g/mol, preferably having an isocyanate content in the rangefrom 20 to 28% by weight, in particular 23% by weight, for exampleLupranat® MP 102 (BASF Aktiengesellschaft), and/or a trimerizedhexamethylene diisocyanate, preferably having an isocyanate content inthe range from 20 to 28% by weight, in particular 23% by weight, forexample Basonat® HI 100 (BASF Aktiengesellschaft).

To produce the thermoplastic polyurethane (i) comprising theisocyanates, it is possible to use generally known thermoplasticpolyurethanes, e.g. ones based on aliphatic or aromatic startingsubstances. The thermoplastic polyurethanes into which the isocyanatesare introduced and which subsequently represent the inventivethermoplastic polyurethanes (i) comprising the isocyanates can have agenerally known hardness. However, preference is given, in particular,to thermoplastic polyurethanes having a Shore hardness of from 80 A to60 D, particularly preferably from 85 A to 95 A, in particular from 90 Ato 95 A, as starting material for producing the concentrates (i).Thermoplastic polyurethanes in the preferred hardness ranges forproducing the inventive thermoplastic polyurethanes (i) comprising theisocyanates are optimized in respect of two aspects: firstly, theisocyanate is dissolved predominantly in the soft phase so that the TPUshould be as soft as possible in order to dissolve a large amount ofisocyanate in the TPU. Secondly, the TPU should be sufficientlyfree-flowing after the incorporation. This is achieved by the TPU beingsufficiently hard for the hard phase to be able to crystallizesufficiently quickly after incorporation of the isocyanate.

The thermoplastic polyurethane (i) comprising the isocyanates ispreferably in the form of pellets, preferably pellets having a preferredmean particle diameter of from 0.05 mm to 10 mm, preferably from 1 mm to5 mm.

The production of the inventive thermoplastic polyurethane (i)comprising isocyanate can be carried out by melting thermoplasticpolyurethane and subsequently incorporating the isocyanate intothermoplastic polyurethane melt, preferably homogeneously. The resultingthermoplastic polyurethane melt (i) should preferably have a temperaturein the range from 120° C. to 160° C. Particular preference is given tomelting the thermoplastic polyurethane at a temperature of from 170° C.to 280° C., preferably from 170 to 240° C., and subsequently mixing theisocyanate at a temperature of from 20 to 80° C. into this melt so thatthe resulting mixture has a temperature of less than 160° C., preferablyin the range from 120° C. to 160° C. Such processing at a targettemperature of less than 160° C. offers the advantage that degradationof the thermoplastic polyurethane caused by the addition ofdiisocyanates or crosslinking of the thermoplastic polyurethane due tothe introduction of triisocyanates or polyisocyanates can be avoided atthis temperature.

The isocyanate can preferably be incorporated into the thermoplasticpolyurethane by means of an extruder, preferably by means of atwin-screw extruder.

The product obtainable from the extruder, i.e. the thermoplasticpolyurethane (i) comprising isocyanate, can preferably be cooled in awater bath immediately after leaving the die of the extruder and thestrand obtained can subsequently be pelletized, for example, by means ofgenerally known methods.

As an alternative, the product obtainable from the extruder, i.e. theTPU melt (i) comprising the isocyanate, can preferably be extrudedthrough a multihole die directly from the extruder into a water bath andsubsequently cut up by means of a rotating knife (underwaterpelletization). Here, the TPU melt (i) is preferably extruded in thewater, preferably through a multihole die, and cut up by means of arotating knife, preferably in the water.

As indicated at the outset, the invention also provides processes forproducing polyurethanes, for example crosslinked or thermoplastic,compact or cellular, rigid, semirigid or flexible polyurethanes whichmay, if appropriate, comprise urea and/or isocyanurate groups, with theproduction being carried out in the presence of the thermoplasticpolyurethanes (i) of the invention. Here, the thermoplasticpolyurethanes (i) comprising the isocyanates are used as isocyanateconcentrate, effectively as sole or additional isocyanate component, ifappropriate in addition to further customary isocyanates. The productionof polyurethanes, for example crosslinked or thermo-plastic, compact orcellular, rigid, semirigid or flexible polyurethanes which may, ifappropriate, comprise urea and/or isocyanurate groups is generally knownand has been described widely. Processes for producing polyurethanes areusually carried out by reacting (a) isocyanates with (b) compounds whichare reactive toward isocyanates, preferably by reacting (a) isocyanateswith (b) compounds having hydrogen atoms which are reactive towardisocyanate groups, preferably in the presence of catalysts (d), (f)physical and/or chemical blowing agents and, if appropriate, (e)additives, and are generally known. The process of the invention isdistinguished from these known processes by, as indicated, the inventivethermoplastic polyurethanes (i) comprising the isocyanates being used asisocyanate (a).

As described at the outset, the invention also provides, in particular,processes for reacting thermoplastic polyurethanes with isocyanate, withthe inventive thermoplastic polyurethane (i) comprising isocyanatesbeing used as isocyanate. In this process, two different thermoplasticpolyurethanes are thus used: firstly, the thermoplastic polyurethanewhich is usually in pelletized or molten form and is to be crosslinkedby the addition of isocyanates and, secondly, the inventivethermoplastic polyurethane (i) comprising the isocyanates, i.e. theisocyanate concentrate, which is added to the TPU to be crosslinked.

As a result of the excess of isocyanate groups produced by the additionof the thermoplastic polyurethane (i) comprising the isocyanates to thethermoplastic polyurethane, these isocyanate groups form crosslinks inthe form of, for example, urethane, allophanate, uretdione and/orisocyanurate structures and possibly urea and biuret bonds during and/orafter mixing of the TPU with the thermoplastic polyurethane (i) in thecold or preferably hot, particularly preferably molten, state of thecomponents, leading to improved properties of the polyisocyanatepolyaddition products. The formation of the crosslinks can, ifappropriate, be promoted by addition of catalysts which are generallyknown for this purpose, for example alkali metal acetates and/orformates. In addition, crosslinking by free isocyanate-reactive groups,e.g. hydroxyl groups of primary or secondary amino groups, in particularhydroxyl groups, of the linear TPU polymer also occurs. These reactivegroups can be present originally in the TPU granules, but they are alsoformed in the TPU melt in the extruder, e.g. by thermal dissociation ofthe polymer strand under processing conditions or during storage orheating of the isocyanate-rich material.

Preference is given to using from 1 to 70 parts by weight, preferablyfrom 5 to 60 parts by weight, particularly preferably from 10 to 50parts by weight, of thermoplastic polyurethane (i) comprisingisocyanates per 100 parts by weight of thermoplastic polyurethane. Theaddition of even small proportions of the concentrate can be useful tocompensate for fluctuations in the composition of TPU batches byaddition of small amounts of isocyanate.

The concentrate (i) is preferably added to the thermoplasticpolyurethane by introducing preferably pelletized thermoplasticpolyurethane, i.e. the thermoplastic polyurethane into which isocyanategroups are to be introduced by means of the concentrate (i), togetherwith the preferably pelletized thermoplastic polyurethane (i), i.e. theconcentrate comprising the isocyanate, into an extruder and melting andmixing them, preferably in the molten state.

As an alternative, it is also possible to introduce the thermoplasticpolyurethane into the extruder, melt it and subsequently add concentrate(i), preferably as pellets, to the melt.

The pelletized thermoplastic polyurethane can be introduced togetherwith the thermoplastic polyurethane (i) into the extruder, preferably bymeans of a feeding aid. The extruder preferably has a barrier screw.

The preferred use of a feeding aid on the extruder or on theinjection-molding apparatus through which the TPU and the thermoplasticpolyurethane (i) comprising the isocyanates are fed into the extrudermakes it possible to introduce the solid TPU pellets quickly andreliably into the extruder or the injection-molding apparatus, eithertogether with or separately from, preferably together with, thethermoplastic polyurethane (i) comprising the isocyanates. Thethermoplastic polyurethane (i) is particularly preferably introducedtogether with thermoplastic polyurethanes through the feeding aid intothe extruder or the injection-molding apparatus, i.e. the same feedingaid is used for the TPU and the thermoplastic polyurethane (i).

The extruder can be a generally known extruder as is generally known,for example, for the extrusion of TPU, e.g. a single- or preferablytwin-screw extruder, particularly preferably a single-screw extruderwith feeding aid, in particular a grooved feeding aid. Theseparticularly preferred configurations lead to particularly effective andeconomical mixing and reaction of TPU with the isocyanates comprised inthe thermoplastic polyurethane (i).

Feeding aids for extruders are generally known to those skilled in theart of extrusion and have been described widely. The feeding aid ispreferably a grooved feed zone. Grooved feeding aids, grooved-barrelextruders or extruders having a grooved feed zone are generally known tothose skilled in the art of extruder technology and have been describedwidely, for example in “Der Extruder im Extrusionsprozeβ—Grundlage fürQualität und Wirtschaftlichkeit”, VDI-Verlag GmbH, Düsseldorf, 1989,ISBN 3-18-234141-3, pages 13 to 27. A characteristic of a grooved feedzone is the presence of longitudinal grooves in the barrel wall whichare usually essentially parallel to the longitudinal extension of thescrew in the feed zone of the extruder and usually taper conically inthe transport direction to the end of the feed zone.

The grooves preferably have a depth which is in the range from 10% to90% of the mean particle diameter of the TPU, i.e. the depth of thegrooves is significantly smaller than the mean particle diameter of thepelletized TPU. The grooves particularly preferably have a depth of from1 mm to 8 mm, preferably from 2 mm to 5 mm. The grooved feed zonepreferably has a length in the range from 2 times to 4 times the screwdiameter. The grooved feed zone preferably has from 4 to 32 grooves,particularly preferably from 4 to 16 grooves, which preferably runparallel or helically, preferably parallel, relative to the longitudinalaxis of the extruder.

As screws, it is possible to use generally known screws, e.g. 3- or5-zone screws. Particular advantages are obtained in the present processwhen an extruder which has a barrier screw is used. Barrier screws aregenerally known in extrusion, e.g. from “Der Extruder imExtrusionsprozeβ—Grundlage für Qualität und Wirtschaftlichkeit”,VDI-Verlag GmbH, Düsseldorf, 1989, ISBN 3-18-234141-3, pages 107 to 125,pages 139 to 143.

The temperature of the melt in the extruder or in the injection-moldingapparatus, preferably the extruder, is usually from 150° C. to 240° C.,preferably from 180° C. to 230° C.

The residence time of the TPU in the extruder is preferably from 120 sto 600 s.

In addition, the present invention provides processes for injectionmolding thermoplastic polyurethane, in which thermoplastic polyurethaneto which isocyanate is to be added by means of the concentrate (i) andwhich is usually to be crosslinked by means of these isocyanate groupsafter injection molding is injection molded together with the inventivethermoplastic polyurethane (i) comprising isocyanates. The concentrateof the invention, i.e. the thermoplastic polyurethane (i) comprising theisocyanate, has the particular advantage of solids metering forinjection molding. The solid concentrates (i) enable liquid isocyanatesto be dispensed with. Nevertheless, a high content of free isocyanategroups can be introduced into the injection-molded shaped body by meansof the concentrate (i). This content of free isocyanate groups cansubsequently be utilized as desired for crosslinking.

In addition, particular preference is given to processes for injectionmolding thermoplastic polyurethane, in which thermoplastic polyurethaneis injection molded as one component in two-component injection moldingtogether with thermoplastic polyurethane (i) comprising isocyanates andis preferably injection molded onto a further thermoplastic polymer,preferably in an adhering fashion.

The injection molding of thermoplastic polymers is generally known andhas been widely described, in particular for thermoplastic polyurethane,too. Thus, the principle of two-component (2-C) injection molding isshown in FIG. 2 in Simon Amesöder et al., Kunststoffe 9/2003, pages 124to 129.

The temperature in the injection molding of thermoplastic polyurethaneis preferably from 140° C. to 250° C., particularly preferably from 160°C. to 230° C. TPUs are preferably processed under mild conditions. Thetemperatures can be adapted depending on the hardness. Thecircumferential velocity during plasticization is preferably less thanor equal to 0.2 m/s, and the back pressure is preferably from 30 to 200bar. The injection velocity is preferably small in order to keep theshear stress low. The cooling time is preferably chosen so as to besufficiently long, with the hold pressure preferably being from 30 to80% of the injection pressure. The molds are preferably heated to from30° C. to 70° C. The gate is preferably chosen at the thickest part ofthe component. In the case of wide-area overinjections, an injectionpoint cascade can be used.

As further thermoplastic polymers, preferably rigid thermoplasticpolymers, it is generally possible to use known further thermoplasticpolymers, for example polyamides, polyesters, polycarbonates, ABS,together with the TPU. Preference is given to firstly producing themolding from a rigid thermoplastic polymer by means of injection moldingand subsequently injection molding the thermoplastic polyurethanecomprising the concentrate (i) onto this.

The injection-molded articles which can be obtained according to theinvention, in particular the articles which preferably comprisepolyurethane adhering to a further thermoplastic polymer and can beobtained by two-component injection molding, have the particularadvantage that they can be crosslinked via the free isocyanate groups.In addition, due to the isocyanates introduced via the concentrate (i),the thermoplastic polyurethane adheres particularly well to furthergenerally known thermoplastic polymers which are used together with thethermoplastic polyurethane in 2-component injection molding.

The process product according to the invention, i.e. the TPU comprisingthe thermoplastic polyurethane (i) with the isocyanate, can be processedby generally known methods, e.g. by means of injection molding orextrusion, to produce moldings of all types, rollers, shoe soles,cladding in automobiles, hoses, cable plugs, bellows, towing cables,wiper blades, cable sheathing, gaskets, belts or damping elements, filmsor fibers. The processing temperature in production of the films,moldings or fibers is preferably from 150° C. to 230° C. particularlypreferably from 180° C. to 220° C. Processing of the mixture to producethe desired films, moldings and/or fibers is preferably carried outimmediately after or during the mixing of the TPU with the thermoplasticpolyurethane (i), since thermoplastic processing of polyisocyanatepolyaddition products to produce films, moldings or fibers is preferablycarried out before and/or during formation of the crosslinks.

The process products from extrusion, injection molding or melt spinning,for example the moldings, films or fibers, can subsequently be heattreated/stored at a temperature of, for example, from 20° C. to 100° C.for a period of usually at least 2 hours, preferably from 12 to 48hours, to form allophanate, uretdione and/or isocyanurate crosslinks,possibly also urea bonds and biurets by hydrolysis, by means of theisocyanate groups present in excess in the polyisocyanate polyadditionproducts. These crosslinks lead to the very advantageous properties ofthe products in respect of thermal stability and hysteresis behaviorafter loading.

Particular preference is also given to processes for producingpreferably transparent, preferably printed films, in which athermoplastic polyurethane is extruded together with the thermoplasticpolyurethane (i) comprising isocyanates. The production of films basedon TPU is generally known and has been described widely.

Particular preference is given to skis which have these films accordingto the invention, in particular as supports for the ski decor. Thesepreferably transparent films are printed on the reverse side andsubsequently adhesively bonded to the ski support. The advantage of theTPU film is the particularly good abrasion resistance, cold flexibilityand high transparency. A ski produced in this way no longer has to beafter-treated.

The particular advantage of the films of the invention is particularlyapparent in the case of printed films. Here, various printing techniquescan be used: thermosublimation printing, screen printing and digitalprinting. Thermosublimation printing has hitherto not been possible forTPU films. The sublimation dye runs further into the matrix afterprinting and the printing becomes blurred very quickly. The addition ofthe TPU concentrate (i) comprising isocyanate to the TPU and thus theincorporation of isocyanate groups into the TPU film enables themigration of the printing ink in the film and thus a blurred printedimage to be prevented. This advantage, i.e. the effective prevention ofthe migration of the dye, is particularly useful when using amine dyes.

Examples of possible binders for dye (donor layer) are: starch,cellulose, agar, porous materials, hydrolyzed PVC-PVA or PVA(EP0531579B1 and U.S. Pat. No. 6,063,842). As dyes, it is possible touse, for example, anthraquinone dyes, monoazo and azomethine dyes(preferably having amino, alkoxy, oxalyl, halogen and cyano groups),leuco bases such as diphenylamines which are oxidized to amino quinones(leuco base=general redox system). Possible binders on paper/carrierfilm are, for example, ZnO, CaCO₃, polyvinyl alcohol, cellulose, metalsalts, metal sulfides, TiO₂ or SiO₂, with this also serving as whitepigment for improving the contrast and also as filler to make thematerial opaque.

The present invention therefore also provides skis which preferably havea transparent, printed, preferably by means of amine dyes, preferably bymeans of thermosublimation printing, film based on a thermoplasticpolyurethane comprising isocyanate, preferably a thermoplasticpolyurethane (i) comprising isocyanate, on at least part of theirvisible surface.

It is possible to use generally known TPUs as TPUs both for producingthe inventive TPU (i) and for crosslinking, i.e. for mixing with theinventive thermoplastic polyurethanes (i) comprising isocyanates. TheTPUs can be used in customary form, preferably granulated material orpellets, preferably granulated material, in the process of theinvention. TPUs are generally known and have been described widely.

Processes for producing TPU are generally known. For example, thethermoplastic polyurethanes can be produced by reacting (a) isocyanateswith (b) compounds which are reactive toward isocyanates and have amolecular weight of from 500 to 10 000 and, if appropriate, (c) chainextenders having a molecular weight of from 50 to 499, if appropriate inthe presence of (d) catalysts and/or (e) customary auxiliaries.

The starting components and processes for producing the preferred TPUsare presented below by way of example. The components (a), (b), (c) and,if appropriate, (d) and/or (e) usually used in the production of TPUsare described by way of example below:

-   -   a) As organic isocyanates (a), it is possible to use generally        known aromatic, aliphatic, cycloaliphatic and/or araliphatic        isocyanates, preferably diisocyanates, for example        diphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI),        naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and/or        2,6-diisocyanate (TDI), diphenylmethane diisocyanate,        3,3′-dimethylbiphenyl diisocyanate, 1,2-diphenylethane        diisocyanate and/or phenylene diisocyanate, trimethylene,        tetramethylene, pentamethylene, hexamethylene, heptamethylene        and/or octamethylene diisocyanate, 2-methylpentamethylene        1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate,        pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate,        1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane        (isophorone diisocyanate, IPDI), 1,4- and/or        1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane        1,4-diisocyanate, 1-methylcyclohexane 2,4- and/or        -2,6-diisocyanate and/or dicyclohexylmethane 4,4′-, 2,4′- and        2,2′-diisocyanate, preferably diphenylmethane 2,2′-, 2,4′-        and/or 4,4′-diisocyanate (MDI), naphthylene 1,5-diisocyanate        (NDI), tolylene 2,4- and/or 2,6-diisocyanate (TDI),        hexamethylene diisocyanate and/or IPDI, in particular 4,4′-MDI        and/or hexamethylene diisocyanate.    -   b) As compounds (b) which are reactive toward isocyanates, it is        possible to use generally known compounds which are reactive        toward isocyanates, for example polyesterols, polyetherols        and/or polycarbonatediols, which are usually collectively        referred to as “polyols”, having molecular weights of from 500        to 12 000 g/mol, preferably from 600 to 6000 g/mol, in        particular from 800 to 4000 g/mol, and preferably a mean        functionality of from 1.8 to 2.3, preferably from 1.9 to 2.2, in        particular 2.    -   c) As chain extenders (c), it is possible to use generally known        aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds        having a molecular weight of from 50 to 499, preferably        2-functional compounds, for example diamines and/or alkanediols        having from 2 to 10 carbon atoms in the alkylene radical, in        particular 1,4-butanediol, 1,6-hexanediol, and/or dialkylene,        trialkylene, tetraalkylene, pentaalkylene, hexaalkylene,        heptaalkylene, octaalkylene, nonaalkylene and/or decaalkylene        glycols having from 3 to 8 carbon atoms, preferably        corresponding oligopropylene glycols and/or polypropylene        glycols, with mixtures of chain extenders also being able to be        used.    -   d) Suitable catalysts which, in particular, accelerate the        reaction between the NCO groups of the diisocyanates (a) and the        hydroxyl groups of the formative components (b) and (c) are the        known and customary tertiary amines such as triethylamine,        dimethylcyclohexylamine, N-methylmorpholine,        N,N′-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol,        diazabicyclo[2,2,2]octane and the like and also, in particular,        organic metal compounds such as titanic esters, iron compounds        such as iron(III) acetylacetonate, tin compounds, e.g. tin        diacetate, tin dioctoate, tin dilaurate or the dialkyltin salts        of aliphatic carboxylic acids, e.g. dibutyltin diacetate,        dibutyltin dilaurate or the like. The catalysts are usually used        in amounts of from 0.00001 to 0.1 part by weight per 100 parts        by weight of polyhydroxyl compound (b),    -   e) Apart from catalysts (d), customary auxiliaries (e) can also        be added to the formative components (a) to (c). Mention may be        made of, for example, surface-active substances, flame        retardants, nucleating agents, oxidation stabilizers, lubricants        and mold release agents, dyes and pigments, stabilizers, e.g.        against hydrolysis, light, heat or discoloration, inorganic        and/or organic fillers, reinforcing materials and plasticizers.        As hydrolysis inhibitors, preference is given to using        oligomeric and/or polymeric aliphatic or aromatic carbodiimides.        To stabilize the TPUs of the invention against aging,        stabilizers are preferably added to the TPU. Stabilizers for the        purposes of the present invention are additives which protect        the polymer or polymer mixture against damaging environmental        influences. Examples are primary and secondary antioxidants,        hindered amine light stabilizers, UV absorbers, hydrolysis        inhibitors, quenchers and flame retardants. Examples of        commercial stabilizers are given in Plastics Additive Handbook,        5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001        ([1]), p. 98-p. 136. If the TPU of the invention is subjected to        thermal oxidative damage during use, antioxidants can be added.        Preference is given to using phenolic antioxidants. Examples of        phenolic antioxidants are given in Plastics Additive Handbook,        5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001,        pp. 98-107 and pp. 116-121. Preference is given to phenolic        antioxidants whose molecular weight is greater than 700 g/mol.        An example of a preferred phenolic antioxidant is        pentaerythrityl        tetrakis(3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate)        (Irganox® 1010). The phenolic antioxidants are generally used in        concentrations of from 0.1 to 5% by weight, preferably from 0.1        to 2% by weight, in particular from 0.5 to 1.5% by weight, in        each case based on the total weight of the TPU. The TPUs are        preferably additionally stabilized by means of a UV absorber. UV        absorbers are molecules which absorb high-energy UV light and        dissipate the energy. Customary UV absorbers which are used in        industry belong, for example, to the group of cinnamic esters,        diphenylcyanoacrylates, formamidines, benzylidenemalonates,        diarylbutadienes, triazines and benzotriazoles. Examples of        commercial UV absorbers may be found in the Plastics Additive        Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers,        Munich, 2001, pages 116-122. In a preferred embodiment, the UV        absorbers have a number average molecular weight of greater than        300 g/mol, in particular greater than 390 g/mol. Furthermore,        the preferred UV absorbers have a molecular weight of not more        than 5000 g/mol, particularly preferably not more than 2000        g/mol. The group of benzotriazoles is particularly useful as UV        absorber. Examples of particularly useful benzotriazoles are        Tinuvin® 213, Tinuvin® 328, Tinuvin® 571 and Tinuvin® 384 and        Eversorb® 82, the UV absorbers are preferably added in amounts        of form 0.01 to 5% by weight, based on the total mass of TPU,        particularly preferably from 0.1 to 2.0% by weight, in        particular from 0.2 to 0.5% by weight, in each case based on the        total weight of the TPU. An above-described UV stabilization        based on an antioxidant and a UV absorber is often not        sufficient to ensure good stability of the TPU of the invention        in the presence of the damaging influence of UV rays. In this        case, a hindered amine light stabilizer (HALS) is preferably        added to the component (e), preferably in addition to the        antioxidant and the UV absorber, to the TPU of the invention.        The activity of HALS compounds is based on their ability to form        nitroxyl radicals which interfere in the mechanism of the        oxidation of polymers. HALSs are highly efficient UV stabilizers        for most polymers. HALS compounds are generally known and        commercially available. Examples of commercially available HALSs        may be found in the Plastics Additive Handbook, 5th edition, H.        Zweifel, Hanser Publishers, Munich, 2001, pp. 123-136. Hindered        amine light stabilizers used are preferably hindered amine light        stabilizers in which the number average molecular weight is        greater than 500 g/mol. Furthermore, the molecular weight of the        preferred HALS compounds should preferably be not more than 10        000 g/mol, particularly preferably not more than 5000 g/mol.        Particularly preferred hindered amine light stabilizers are        bis(1,2,2,6,6-pentamethylpiperidyl) sebacate (Tinuvin® 765, Ciba        Spezialitätenchemie AG) and, the condensation product of        1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and        succinic acid (Tinuvin® 622). Very particular preference is        given to the condensation product of        1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and        succinic acid (Tinuvin® 622) when the titanium content of the        product is <150 ppm, preferably <50 ppm particularly preferably        <10 ppm. HALS compounds are preferably used in a concentration        of form 0.01 to 5% by weight, particularly preferably from 0.1        to 1% by weight, in particular from 0.1 5 to 0.3% by weight, in        each case based on the total weight of the TPU. A particularly        preferred UV stabilization comprises a mixture of a phenolic        stabilizer, a benzotriazole and an HALS compound in the        above-described preferred amounts.

Further details regarding the abovementioned auxiliaries and additivesmay be found in the specialist literature, e.g. Plastics AdditiveHandbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001.All molecular weights mentioned in the present text have the units[g/mol].

To set the hardness of the TPUs, the molar ratios of the formativecomponents (b) and (c) can be varied within a relatively wide range.Molar ratios of component (b) to total chain extenders (c) to be used offrom 10:1 to 1:10, in particular from 1:1 to 1:4, have been found to beuseful, with the hardness of the TPUs increasing with increasing contentof (c).

The reaction can be carried out at customary indexes, preferably at anindex of from 950 to 1050, particularly preferably at an index in therange from 970 to 1010, in particular from 980 to 995. The index isdefined as the molar ratio of the total isocyanate groups of thecomponent (a) used in the reaction to the isocyanate-reactive groups,i.e. the active hydrogens, of the components (b) and (c). At an index of1000, there is one active hydrogen atom, i.e. one isocyanate-reactivefunction, of the components (b) and (c) per isocyanate group of thecomponent (a). At indexes above 1000, there are more isocyanate groupsthan OH groups present. The production of the TPUs can be carried out byknown methods either continuously, for example by means of reactionextruders or the belt process by the one-shot or the prepolymer process,or discontinuously by the known prepolymer process. In these processes,the components (a), (b) and, if appropriate, (c), (d) and/or (e) whichare reacted can be mixed with one another either in succession orsimultaneously, with the reaction commencing immediately. In theextruder process, the formative components (a), (b) and, if appropriate,(c), (d) and/or (e) are introduced individually or as a mixture into theextruder, reacted at, for example, temperatures of from 100° C. to 280°C., preferably from 140° C. to 250° C., and the TPU obtained isextruded, cooled and pelletized.

Owing to the particularly good adhesion, TPUs as described in WO03/014179, are particularly suitable both for producing the concentrates(i) and for mixing with the concentrate (i). The following informationup to the examples is based on this particularly preferred TPU.

These particularly preferred TPUs are preferably obtainable by reacting(a) isocyanates with (b1) polyester diols having a melting point ofgreater than 150° C., (b2) polyether diols and/or polyester diols ineach case having a melting point of less than 150° C. and a molecularweight of from 501 to 8000 g/mol and, if appropriate, (c) diols having amolecular weight of from 62 g/mol to 500 g/mol. Particular preference isgiven to thermoplastic polyurethanes in which the molar ratio of thediols (c) having a molecular weight of from 62 g/mol to 500 g/mol to thecomponent (b2) is less than 0.2, particularly preferably from 0.1 to0.01. Particular preference is given to thermoplastic polyurethanes inwhich the polyester diols (b1), which preferably have a molecular weightof from 1000 g/mol to 5000 g/mol, comprise the following structural unit(I):

where R1, R2, R3 and X have the following meanings:

-   -   R1: carbon skeleton having from 2 to 15 carbon atoms, preferably        an alkylene group having from 2 to 15 carbon atoms and/or a        divalent aromatic radical having from 6 to 15 carbon atoms,        particularly preferably from 6 to 12 carbon atoms,    -   R2: optionally branched alkylene group having from 2 to 8 carbon        atoms, preferably from 2 to 6 carbon atoms, particularly        preferably from 2 to 4 carbon atoms, in particular —CH₂—CH₂—        and/or —CH₂—CH₂—CH₂—CH₂—,    -   R3: optionally branched alkylene group having from 2 to 8 carbon        atoms, preferably from 2 to 6 carbon atoms, particularly        preferably from 2 to 4 carbon atoms, in particular —CH₂—CH₂—        and/or —CH₂—CH₂—CH₂—CH₂—,    -   X: an integer in the range from 5 to 30. The preferred melting        point indicated above and/or the preferred molecular weight are        in this preferred embodiment based on the structural unit (I)        shown.

For the purposes of the present text, the expression “melting point”refers to the maximum of the melting peak of a heating curve measuredusing a commercial DSC instrument (e.g. DSC 7/from Perkin-Elmer).

The molecular weights reported in the present text are the numberaverage molecular weights in [g/mol].

These particularly preferred thermoplastic polyurethanes can preferablybe prepared by reacting a, preferably high molecular weight, preferablypartially crystalline, thermoplastic polyester with a diol (c) in afirst step (I) and subsequently, in a further reaction (II), reactingthe reaction product from (I) comprising (b1) polyester diol having amelting point of greater than 150° C. and, if appropriate, (c) dioltogether with (b2) polyether diols and/or polyester diols in each casehaving a melting point of less than 150° C. and a molecular weight offrom 501 to 8000 g/mol and, if appropriate, further (c) diols having amolecular weight of from 62 to 500 g/mol with (a) isocyanate, ifappropriate in the presence of (d) catalysts and/or (e) auxiliaries.

The molar ratio of the diols (c) having a molecular weight of from 62g/mol to 500 g/mol to the component (b2) in the reaction (II) ispreferably less than 0.2, preferably from 0.1 to 0.01.

While the hard phases are made available for the end product in step (I)by means of the polyester used in step (I), the use of the component(b2) in step (II) results in formation of the soft phases. The preferredtechnical teaching is that polyesters having a pronounced, readilycrystallizing hard phase structure are melted, preferably in a reactionextruder, and firstly degraded by reaction with a low molecular weightdiol to form shorter polyesters having free hydroxyl end groups. Here,the original high crystallization tendency of the polyester is retainedand can subsequently be utilized in a rapidly occurring reaction toobtain TPUs having the advantageous properties such as high tensilestrength, low abrasion values and, because of the high and narrowmelting range, high heat distortion resistances and low compressionsets. Thus, in the preferred process, preferably high molecular weight,partially crystalline, thermoplastic polyesters are degraded in a shortreaction time by reaction with low molecular weight diols (c) undersuitable conditions to give rapidly crystallizing polyester diols (b1)which in turn are then incorporated into high molecular weight polymerchains together with other polyester diols and/or polyether diols anddiisocyanates.

Here, the thermoplastic polyester used, i.e. before the reaction (I)with the diol (c), preferably has a molecular weight of from 1 5 000g/mol to 40 000 g/mol and preferably has a melting point of greater than160° C., particularly preferably from 170° C. to 260° C.

As starting material, i.e. as polyester, which is reacted in step (I),preferably in the molten state, particularly preferably at a temperatureof from 230° C. to 280° C. for a time of preferably from 0.1 min to 4min, particularly preferably from 0.3 min to 1 min, with the diol(s)(c), it is possible to use generally known, preferably high molecularweight, preferably partially crystalline, thermoplastic polyesters, forexample in pelletized form. Suitable polyesters are based, for example,.on aliphatic, cycloaliphatic, araliphatic and/or aromatic dicarboxylicacids, for example lactic acid and/or terephthalic acid, and aliphatic,cycloaliphatic, araliphatic and/or aromatic dialcohols, for example1,2-ethanediol, 1,4-butanediol and/or 1,6-hexanediol.

Particularly preferred polyesters are: poly-L-lactic acid and/orpolyalkylene terephthalate, for example polyethylene terephthalate,polypropylene terephthalate, polybutylene terephthalate, in particularpolybutylene terephthalate.

The preparation of these esters from the starting materials mentioned isgenerally known to those skilled in the art and has been describedwidely. In addition, suitable polyesters are commercially available

The thermoplastic polyester is preferably melted at a temperature offrom 180° C. to 270° C. The reaction (I) with the diol (c) is preferablycarried out at a temperature of from 230° C. to 280° C., preferably from240° C. to 280° C.

As diol (c) for reaction with the thermoplastic polyester in step (I)and if appropriate in step (II), it is possible to use generally knowndiols having a molecular weight of from 62 to 500 g/mol, for example thediols mentioned at a later point, e.g. ethylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, heptanediol,octanediol, preferably 1,4-butanediol and/or 1,2-ethanediol.

The weight ratio of the thermoplastic polyester to the diol (c) in step(I) is usually from 100:1.0 to 100.10, preferably from 100:1.5 to100:8.0.

The reaction of the thermoplastic polyester with the diol (c) inreaction step (I) is preferably carried out in the presence of customarycatalysts, for example those which are described at a later point.Preference is given to using catalysts based on metals for thisreaction. The reaction in step (I) is preferably carried out in thepresence of from 0.1 to 2% by weight of catalysts, based on the weightof the diol (c). The reaction in the presence of such catalysts isadvantageous in order to enable the reaction to be carried out in theshort residence time available in the reactor, for example a reactionextruder.

Possible catalysts for this reaction step (I) are, for example:tetrabutyl orthotitanate and/or tin(II) dioctoate, preferably tindioctoate.

The polyester diol (b1) as reaction product from (I) preferably has amolecular weight of from 1000 g/mol to 5000 g/mol. The melting point ofthe polyester diol as reaction product from (I) is preferably from 150°C. to 260° C., in particular from 165° C. to 245° C., i.e. the reactionproduct of the thermoplastic polyester with the diol (c) in step (I)comprises compounds which have the melting point mentioned and are usedin the subsequent step (II).

In the reaction of the thermoplastic polyester with the diol (c) in step(I), the polymer chain of the polyester is cleaved bytransesterification by means of the diol (c). The reaction product ofthe thermoplastic polyester therefore has free hydroxyl end groups andis preferably processed further in the further step (II) to give theactual product, viz. the TPU.

The reaction of the reaction product from step (I) in step (II) ispreferably carried out by addition of a a) isocyanate (a) and (b2)polyether diols and/or polyester diols in each case having a meltingpoint of less than 150° C. and a molecular weight of from 501 to 8000g/mol and, if appropriate, further diols (c) having a molecular weightof from 62 to 500, (d) catalysts and/or (e) auxiliaries to the reactionproduct from (I). The reaction of the reaction product with theisocyanate occurs via the hydroxyl end groups formed in step (I). Thereaction in step (II) is preferably carried out at a temperature of from190° C. to 250° C. for a time of preferably from 0.5 to 5 min,particularly preferably from 0.5 to 2 min, preferably in a reactionextruder, particularly preferably in the same reaction extruder in whichstep (I) has also been carried out. For example, the reaction of step(I) can be carried out in the first barrel section of a customaryreaction extruder and the corresponding reaction of step (II) can becarried out at a later point, i.e. later barrel sections, after additionof the components (a) and (b2). For example, the first 30-50% of thelength of the reaction extruder can be used for step (I) and theremaining 50-70% can be used for step (II).

The reaction in step (II) is preferably carried out at an excess ofisocyanate groups over the groups which are reactive toward isocyanates.The ratio of isocyanate groups to hydroxyl groups in the reaction (II)is preferably from 1:1 to 1.2:1, particularly preferably from 1.02:1 to1.2:1.

The reactions (I) and (II) are preferably carried out in a generallyknown reaction extruder. Such reaction extruders are described, forexample, in the company brochure of Werner & Pfleiderer or in DE-A 2 302564.

The preferred process is preferably carried out by metering at least onethermoplastic polyester; e.g. polybutylene terephthalate, into the firstbarrel section of a reaction extruder and melting it at temperatures ofpreferably from 180° C. to 270° C., preferably from 240° C. to 270° C.,adding a diol (c), e.g. butanediol, and preferably a transesterificationcatalyst in a subsequent barrel section, degrading the polyester byreaction with the diol (c) at temperatures of from 240° C. to 280° C. toform polyester oligomers having hydroxyl end groups and molecularweights of from 1000 to 5000 g/mol, adding isocyanate (a) and (b2)compounds which are reactive toward isocyanates and have a molecularweight of from 501 to 8000 g/mol and, if appropriate, (c) diols having amolecular weight of from 62 to 500, (d) catalysts and/or (e) auxiliariesin a subsequent barrel section and subsequently carrying out theformation of the preferred thermoplastic polyurethanes at temperaturesof from 190° C. to 250° C.

In step (II), preference is given to feeding in no diols (c) having amolecular weight of from 62 to 500 apart from the diols (c) present inthe reaction product from (i).

The reaction extruder preferably has neutral and/orbackward-transporting kneading blocks and back-transporting elements,preferably screw mixing elements, toothed disks and/or toothed mixingelements in combination with back-transporting elements, in the regionin which the thermoplastic polyester is melted and also in the region inwhich the thermoplastic polyester is reacted with the diol.

After the reaction extruder, the clear melt is usually conveyed by meansof a gear pump to underwater pelletization and pelletized.

The particularly preferred thermoplastic polyurethanes give opticallyclear, single-phase melts which solidify rapidly and, owing to thepartial crystalline polyester hard phase, form slightly opaque to opaquewhite moldings. The rapid solidification behavior is an importantadvantage compared to known formulations and production processes forthermoplastic polyurethanes. The rapid solidification behavior is sopronounced that even products having hardnesses of from 50 to 60 Shore Acan be processed by injection molding with cycle times of less than 35s. In extrusion too, e.g. in blown film production, no problems typicalof TPUs, e.g. conglutination or blocking of the films or film bubbles,occur.

The proportion of thermoplastic polyester in the end product, i.e. thethermoplastic polyurethane, is preferably from 5 to 75% by weight. Thepreferred thermoplastic polyurethanes are particularly preferablyproducts of the reaction of a mixture comprising form 10 to 70% byweight of the reaction product from (I), from 10 to 80% by weight of(b2) and from 10 to 20% by weight of (a), with the percentages by weightbeing based on the total weight of the mixture comprising (a), (b2),(d), (e) and the reaction product from (I).

The preferred thermoplastic polyurethanes preferably have a hardness offrom Shore 45 A to Shore 78 D, particularly preferably from 50 A to 75D.

The preferred thermoplastic polyurethanes preferably comprise thefollowing structural unit (II):

where R1, R2, R3 and X have the following meanings:

-   -   R1: carbon skeleton having from 2 to 1 5 carbon atoms,        preferably an alkylene group having from 2 to 15 carbon atoms        and/or an aromatic radical having from 6 to 15 carbon atoms,    -   R2 : optionally branched alkylene group having from 2 to 8        carbon atoms, preferably from 2 to 6 carbon atoms, particularly        preferably from 2 to 4 carbon atoms, in particular —CH₂—CH₂—        and/or —CH₂—CH₂—CH₂—CH₂—,    -   R3: a radical which is formed by use of polyether diols and/or        polyester diols in each case having molecular weights of from        501 g/mol to 8000 g/mol as (b2) or by use of alkanediols having        from 2 to 12 carbon atoms for the reaction with diisocyanates,    -   X: an integer in the range from 5 to 30,    -   n, m: each an integer in the range from 5 to 20.

The radical R1 is defined by the isocyanate used, the radical R2 isdefined by the reaction product of the thermoplastic polyester with thediol (c) in (1) and the radical R3 is defined by the starting components(b2) and, if appropriate, (c) in the production of the TPU.

EXAMPLES

In the examples described below, the following isocyanates andthermoplastic polyurethanes (TPUs) were used:

Isocyanates

-   -   Lupranat® MM 103: Carbodiimide-modified diphenyl methane        4,4′-diisocyanate (MDI); NCO content: 29.5% by weight    -   Lupranat® MP 102: Prepolymer based on MDI, dipropylene glycol        and a polyether diol based on ethylene oxide/propylene oxide        having a molecular weight of 450; NCO content: 23.0% by weight    -   Basonat® H 100: Trimerized hexamethylene diisocyanate; NCO        content 22.0% by weight

Thermoplastic Polyurethanes (TPUs)

-   -   Elastollan® C 78 A, Polyester polyurethanes based on MDI,        1,4-butanediol as C 80 A, C 85 A: chain extender and polyester        diol (butanediol-hexanedioladipic acid copolyester) having a        molecular weight of 2000.    -   Elastollan® 1195 A, Polyether polyurethanes based on MDI,        1,4-butanediol as 1154 D, 1174 D: chain extender and        polytetramethylene glycol having a molecular weight of 1000.    -   Elastollan® C85 A Hard phase-modified polyester polyurethane        based on MDI, 15 HPM: 1,4-butanediol, polyester diol as in the        case of Elastollan® C grades and a polybutylene terephthalate        segment as hard phase.

Example 1

polyurethanes (i) according to claim 1, a twin-screw extruder model ZE40 A from Berstorff having a process section length of 35 D divided into10 barrels was used. The screw element arrangement had twobackward-conveying kneading blocks as melting unit for the TPU pelletsin barrel 2. Barrel 3 comprised a facility for adding liquid isocyanatesto the TPU melt. Barrels 3, 6 and 7 had mixing elements in the form ofserrated disk blocks in addition to conventional transport elements.

The barrel temperatures were initially all set to 210° C. and 15.0 kg/hof Elastollan® C 85 A pellets were fed continuously by gravimetricmetering into barrel 1. 5.0 kg/h of Lupranat® MM 103 were thenintroduced continuously into the TPU melt by means of a gear pump andgravimetric metering into barrel 3 and intensively mixed in in thesubsequent barrels. After the addition of Lupranat® MM 103, all furtherbarrel temperatures from barrel 4 onward were reduced to 150° C. Afterthe optically clear strands of melt leaving the extruder die head hadreached temperatures of 150-160° C., they were cooled in a water bath,freed of adhering water in an extraction apparatus and pelletized in theusual way. This resulted in hard, nonsticky granules which crystallizedreadily and could be used without after-drying (concentrate No. 1).

Example 2

Using the same extruder setup and the same mode of operation, 12.0 kg/hof Elastollan C 85 A were mixed with 8.0 kg/h of a liquid isocyanatemixture of 80% of Lupranat® MP 102 and 20% of Basonat® H 100 andpelletized. (Concentrate No. 2)

TABLE 1 NCO content Concen- (% by weight) trate Composition theoreticalfound No. 1 EC 85 A + 25% of Lupranat ® MM 103 7.5 7.0 No. 2 EC 85 A +32% of Lupranat ® 9.1 8.7 MP 102 + 8% of Basonat ® M 100

The reduced NCO content determined by analysis can be explained by waterremaining in the pelletized material in an amount of 0.05-0.15% byweight leading to a reduction in the NCO content by reacting with NCOgroups.

Example 3

To produce the inventive thermoplastic polyurethanes (i) according toclaim 1, a twin-screw extruder model ZSK 58 from Werner & Pfleidererhaving a process section length of 48 D divided into 12 barrels wasused. The melt was discharged from the extruder by means of a heatedgear pump, and pelletization was effected by means of a conventionalunderwater pelletization apparatus (UWP). The screw element arrangementcorresponded to the arrangement described in example 1.

All barrel temperatures were initially set to 210° C. and 75.0 kg/h ofElastollan® C 85 A were continuously metered gravimetrically into barrel1, melted, discharged from the extruder via the gear pump which hadlikewise been heated to 210° C. and pelletized in the UWP in order todetermine the molecular weight of the extruded EC 85 A material.

75.0 kg of Lupranat® MP 102 were then continuously added gravimetricallyto the TPU melt in barrel 5, mixed in and discharged without reducingthe temperature. Owing to the extraordinarily low melt viscosity,underwater pelletization was not possible. However, a sample was takenin order to determine the molecular weight reduction (concentrate No.3).

The barrel temperatures after barrel 5 and the temperature of the gearpump were subsequently reduced to 140° C. After the optically clear meltbeing discharged had likewise reached temperatures of 140-145° C.,problem-free underwater pelletization was possible. The pellets obtainedwere freed of water adhering to the surface in a centrifuge andcollected without further drying (concentrate No. 4).

TABLE 2 NCO content Molecular Concen- (% by weight) weight Mn trateComposition theoretical found in dalton EC 85 A extruded at melt — 0.1034900 temperature of 210° C. No. 3 EC 85 A + 50% of Lupranat ® 11.5 10.815000 MP 102 extruded at melt temperature of 210° C. No. 4 EC 85 A + 50%of Lupranat ® 11.5 9.9 33100 MP 102 extruded at melt temperature of 140°C.

The molecular weights Mn were determined in a customary way by means ofgel permeation chromatography using dimethylformamide as solvent/eluentand mass calibration using narrow-distribution polymethyl methacrylate.

Example 4

Elastollan® C 80 A 10 pellets were mixed with pellets of concentrate No.1 and concentrate No. 4 and these pellet mixtures were processed in acustomary manner by injection molding to produce test plates, the testplates were heat treated at 100° C. for 20 hours and the mechanicalproperties were determined.

To test the storage stability of such isocyanate-rich concentrates, acomparable mixing trial using Elastollan® C 80 A 10 was carried outafter storage of concentrate No. 4 for four months.

The results are described in table 3.

TABLE 3 Proportion in the mixture (% by weight) Concentrate No. 1Concentrate No. 4 Property Unit Test method 0 4 5 6 8 4 5 Hardness ShoreDIN 53 505 83 A 84 A 84 A 84 A 84 A 82A 83 A Density g/cm³ DIN EN ISO1.181 1.182 1.184 1.185 1.186 1.184 1.184 1183-1 Tensile strength MPaDIN 53 504 47 48 50 52 51 50 51 Elongation at break % DIN 53 504 620 560550 530 540 520 520 Abrasion mm³ DIN 53 516 32 30 31 32 30 28 30Compression set 72 h/23° C. % DIN ISO 815 19 17 18 19 19 17 16 24 h/70°C. 31 29 26 27 25 26 21 24 h/100° C. 55 50 47 39 39 44 40 Vicat A 120 °C. DIN EN ISO 306 110 125 130 134 136 129 130 Proportion in the mixtureConcentrate No. 4 (% by weight) Concentrate No. 4 after storage for 4months Property Unit Test method 6 8 4 5 6 8 Hardness Shore DIN 53 50583 A 84 A 83 A 84 A 84 A 85 A Density g/cm³ DIN EN ISO 1.184 1.186 1.1841.184 1.184 1.186 1183-1 Tensile strength MPa DIN 53 504 56 51 48 49 5148 Elongation at break % DIN 53 504 540 500 540 510 500 490 Abrasion mm³DIN 53 516 32 30 30 32 29 33 Compression set 72 h/23° C. % DIN ISO 81516 20 20 17 18 18 24 h/70° C. 21 20 26 26 26 24 24 h/100° C. 38 37 48 4543 41 Vicat A 120 ° C. DIN EN ISO 306 132 136 125 126 127 133

The changes in the mechanical properties resulting from addition of theisocyanate concentrates are a reduction in the elongation at break, adecrease in the compression set values, in particular at 100° C., and anincrease in the heat distortion resistance, measured by the VICAT A 120value.

These effects are based on crosslinking of the Elastollan® C 85 A 10resulting from addition of isocyanate.

Furthermore, comparison of the effects of concentrate No. 4 andconcentrate No. 4 after storage for 4 months showed that thethermoplastic polyurethanes (i) of the invention will keep without lossof effectiveness when stored correctly.

Example 5

Elastollan® C 85 A 15 HPM pellets were mixed with concentrate No. 4,processed and tested in the same way as described in example 4.

TABLE 4 Proportion (% by weight) Concentrate No. 4 Property Unit Testmethod 0 4 5 6 8 Hardness Shore DIN 53 505 84 A 86 A 86 A 87 A 87 ADensity g/cm³ DIN EN ISO 1.194 1.196 1.196 1.198 1.198 1183-1 Tensilestrength MPa DIN 53 504 35 41 43 43 45 Elongation at break % DIN 53 504750 730 680 640 600 Abrasion mm³ DIN 53 516 40 35 33 30 34 Compressionset 72 h/23° C. % DIN ISO 815 15 17 18 16 18 24 h/70° C. 25 28 26 27 2324 h/100° C. 50 42 45 43 46 Vicat A 120 ° C. DIN EN ISO 306 120 134 136138 142

The results show that the mode of action of the polyurethanes (i) of theinvention on addition to TPU modified with hard phase are comparablewith the effects when using TPU having a structure corresponding to theElastollan® C grades.

Example 6

Concentrate No. 4 obtained as described in example 3 was fed as a pelletmixture with Elastollan® 1195 A and Elastollan® 1154 D into an extruderhaving a groove feed zone, process section length of 32 D and a barriermixing part screw, melted, mixed and extruded as a tube. Extrudateshaving a smooth surface were obtained.

To determine the degree of crosslinking, Elastollan® 1195 A and 1154 Dwere extruded in the same way without addition of concentrate No. 4.About 4 g of the extrudates were stirred in 50 ml of dimethylformamidefor 14 hours and the proportions of soluble material were subsequentlydetermined.

TABLE 5 Concentrate No. 4 Proportion in the mixture Proportion ofsoluble (% by weight) Elastollan ® grade material (% by weight) 0 1195 A100% 8 1195 A 60% 0 1154 D 100% 8 1154 D 55%

Example 7

Elastollan® 1174 D was processed in a customary manner by injectionmolding to produce plates. These plates were then printed using athermotransfer color film (amine-comprising) for 2 minutes at 180° C.and cooled again. The plates prepared in this way were subsequentlystored at 80° C. for 3 days. Diffusion of the dye of about 800 μm wasdetermined on cross sections of these plates by means of opticalmicroscopy. The printed image was blurred after the hot storage.

Example 8

Elastollan® 1174 D with addition of 5% of concentrate No. 4 obtained asdescribed in example 3 was likewise processed as a pellet mixture byinjection molding to produce plates, printed using thermotransfer colorfilm and stored at 80° C. for 3 days in the same way as described inexample 7.

Diffusion of the dye of about 300 μm was determined on cross sections ofthese plates by means of optical microscopy. The printed image was sharpand had not run even after hot storage.

Example 9

Ultramid® B3, viz. a polyamide 6 from BASF, was shaped on atwo-component injection molding machine to produce a plate havingdimensions of 4×65×130 mm and Elastollan® C 78 A 10 as soft componentwas subsequently injected onto this hard Ultramid® B3 plate so that thetwo equal-sized plates were joined to one another over thecross-sectional area of 4×130 mm. Test bars S1 in accordance with DIN 53504 were milled from these plates so that the interface was precisely inthe middle of the S1 bar.

The tensile strength, i.e. the bond strength between Ultramid® B3 andElastollan® C 78 A 10, was then tested in accordance with DIN 53 504.

The same procedure was also carried out for pellet blends of Elastollan®C 78 A 10 and concentrate No. 4 as soft component for injection ontoUltramid® B3.

TABLE 6 Bond strength (MPa) heat treated at Soft component not heattreated 100° C./20 h C 78 A 10 without additive 7.5 10.0 C 78 A 10 + 1%of concentrate No. 4 8.0 10.8 C 78 A 10 + 2% of concentrate No. 4 8.511.5 C 78 A 10 + 3% of concentrate No. 4 9.2 13.5 C 78 A 10 + 4% ofconcentrate No. 4 9.6 16.7

As can be seen from the results, bond strengths of a composite of hardpolyamide 6 and soft TPU can be significantly improved by addition ofthe thermoplastic polyurethanes (i) of the invention. Similar increasescan be achieved when polybutylene terephthalate, polyethyleneterephthalate, polycarbonate, ABS plastics, etc., are used as hardcomponent.

1-21. (canceled)
 22. A thermoplastic polyurethane (i) comprising from20% by weight to 70% by weight of isocyanate dissolved in thethermoplastic polyurethane, based on the total weight of thethermoplastic polyurethane (i) comprising the isocyanates.
 23. Thethermoplastic polyurethane (i) of claim 22, wherein the NCO content ofthe thermoplastic polyurethane (i) comprising the isocyanate is greaterthan 5%.
 24. The thermoplastic polyurethane (i) of claim 22, whereindiphenylmethane 2,2′-, 2,4′- and/or 4,4′-diisocyanate (MDI), acarbodiimide-modified diphenylmethane 2,2′-, 2,4′- and/or4,4′-diisocyanate (MDI), a prepolymer based on diphenylmethane 2,2′-,2,4′- and/or 4,4′-diisocyanate (MDI), isocyanates comprising biuretand/or isocyanurate groups are present as isocyanate in thethermoplastic polyurethane (i).
 25. The thermoplastic polyurethane (i)of claim 22, wherein carbodiimide-modified diphenylmethane4,4′-diisocyanate (MDI), prepolymer based on ethylene oxide/propyleneoxide and/or trimerized hexamethylene diisocyanate are present asisocyanate in the thermoplastic polyurethane (i).
 26. The thermoplasticpolyurethane (i) of claim 22, wherein the thermoplastic polyurethane inwhich the isocyanate is dissolved has a Shore hardness of from 80 A to60 D before incorporation of the isocyanate.
 27. The thermoplasticpolyurethane (i) of claim 22, wherein the thermoplastic polyurethane (i)is in the form of pellets.
 28. A process for producing the thermoplasticpolyurethane (i) comprising isocyanate of claim 22, comprising meltingthe thermoplastic polyurethane and subsequently incorporating theisocyanate into said melt.
 29. The process of claim 28, whereinthermoplastic polyurethane is melted at temperatures of from 170 to 240°C. and the isocyanate at a temperature in the range from 20 to 80° C. issubsequently mixed into this melt so that the resulting mixture has atemperature in the range of from 120 to 160° C.
 30. The process of claim28, wherein the isocyanate is incorporated into the thermoplasticpolyurethane by means of an extruder.
 31. The process of claim 30,wherein the isocyanate is incorporated into the thermoplasticpolyurethane by means of a twin-screw extruder.
 32. The process of claim30, wherein the product obtained from the extruder, i.e., thethermoplastic polyurethane (i) comprising isocyanate, is cooled in awater bath immediately after leaving the die of the extruder and thestrand obtained is subsequently pelletized.
 33. The process of claim 30,wherein the product obtainable from the extruder, i.e., the TPU melt (i)comprising the isocyanate, is extruded through a multihole dye directlyfrom the extruder into a water bath and is subsequently cut up by meansof a rotating knife.
 34. A process for producing polyurethanescomprising reacting (a) isocyanates with (b) compounds which arereactive toward isocyanates, wherein the production is carried out inthe presence of the thermoplastic polyurethanes (i) of claim
 22. 35. Aprocess for reacting thermoplastic polyurethanes with isocyanate,wherein the thermoplastic polyurethane (i) comprising isocyanates ofclaim 22 is used as isocyanate.
 36. The process of claim 35, whereinfrom 1 to 70 parts by weight of thermoplastic polyurethane (i)comprising isocyanates according to any of claims 1 to 6 are used per100 parts by weight of thermoplastic polyurethane.
 37. The process ofclaim 35, wherein the thermoplastic polyurethane (i) is introduced intoan extruder and melted together with the thermoplastic polyurethane. 38.A process for injection molding thermoplastic polyurethane, whereinthermoplastic polyurethane is injection molded together with thethermoplastic polyurethane (i) comprising isocyanates of claim
 22. 39.The process for injection molding the thermoplastic polyurethane ofclaim 38, wherein thermoplastic polyurethane is injection molded bytwo-component injection molding together with a thermoplasticpolyurethane (i) comprising from 20% by weight to 70% by weight ofisocyanate dissolved in the thermoplastic polyurethane, based on thetotal weight of the thermoplastic polyurethane (i) comprising theisocyanates.
 40. An injection-molded article obtained by the process ofclaim
 38. 41. An extruded article obtained by the process of claim 35.42. A film obtained by the process of claim 35